Cross-linked polymersome membranes: Vesicles with broadly adjustable properties

被引:222
作者
Discher, BM
Bermudez, H
Hammer, DA
Discher, DE [1 ]
Won, YY
Bates, FS
机构
[1] Univ Penn, Sch Engn & Appl Sci, Philadelphia, PA 19104 USA
[2] Univ Minnesota, Dept Chem Engn & Mat Sci, Minneapolis, MN 55455 USA
关键词
D O I
10.1021/jp011958z
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Massively cross-linked and property-tunable membranes have been fabricated by free radical polymerization of self-assembled, block copolymer vesicles - polymersomes. Similar efforts with cross-linkable lipids would appear frustrated in the past due to at least two factors: limited reactivity and membrane fragility under local stresses of nano-confined cross-linking. We describe here a diblock copolymer of poly(ethylene oxide)polybutadiene that has a hydrophilic weight fraction like that of lipids and forms robust fluid phase membranes in water. The polymersomes sustain free radical polymerization of the hydrophobic butadiene, thereby generating a semipermeable nano-shell. Cross-linked giant vesicles prove stable in chloroform and can also be dehydrated and re-hydrated without rendering the similar to9 nm thick membrane core; the results imply defect-free membranes many microns-squared in area. Surface elastic moduli as well as sustainable wall stresses up to 10(3) Atm, orders of magnitude greater than any natural lipid membrane, appear consistent with strong tethering between close-packed neighbors. The enormous stability of the giant vesicles can be tuned down for application: blending in the hydrogenated analogue poly(ethylene oxide)-polyethylethylene modulates the effective elastic constants as well as the rupture strength by orders of magnitude. The results appear consistent with rigidity percolation through a finite-layer stack of two-dimensional lattices. Moreover, below the percolation limit, a regime of hyper-instability emerges, reflecting perhaps nanoscale demixing and suggestive of the limitations encountered with low reactivity lipids. The results provide general insights into covalent cross-linking within self-assembled nanostructures.
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收藏
页码:2848 / 2854
页数:7
相关论文
共 34 条
  • [1] Criterion for crack formation in disordered materials
    Arndt, PF
    Nattermann, T
    [J]. PHYSICAL REVIEW B, 2001, 63 (13):
  • [2] PHYSICAL-PROPERTIES OF THE FLUID LIPID-BILAYER COMPONENT OF CELL-MEMBRANES - A PERSPECTIVE
    BLOOM, M
    EVANS, E
    MOURITSEN, OG
    [J]. QUARTERLY REVIEWS OF BIOPHYSICS, 1991, 24 (03) : 293 - 397
  • [3] Polymersomes: Tough vesicles made from diblock copolymers
    Discher, BM
    Won, YY
    Ege, DS
    Lee, JCM
    Bates, FS
    Discher, DE
    Hammer, DA
    [J]. SCIENCE, 1999, 284 (5417) : 1143 - 1146
  • [4] Polymer vesicles in various media
    Discher, BM
    Hammer, DA
    Bates, FS
    Discher, DE
    [J]. CURRENT OPINION IN COLLOID & INTERFACE SCIENCE, 2000, 5 (1-2) : 125 - 131
  • [5] Phase transitions and anisotropic responses of planar triangular nets under large deformation
    Discher, DE
    Boal, DH
    Boey, SK
    [J]. PHYSICAL REVIEW E, 1997, 55 (04) : 4762 - 4772
  • [6] PERMEABILITY CHARACTERISTICS OF POLYMERIC BILAYER-MEMBRANES FROM METHACRYLOYL AND BUTADIENE LIPIDS
    DORN, K
    KLINGBIEL, RT
    SPECHT, DP
    TYMINSKI, PN
    RINGSDORF, H
    OBRIEN, DF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (06) : 1627 - 1633
  • [7] Optically, defined multifunctional patterning of photosensitive thin-film silica mesophases
    Doshi, DA
    Huesing, NK
    Lu, MC
    Fan, HY
    Lu, YF
    Simmons-Potter, K
    Potter, BG
    Hurd, AJ
    Brinker, CJ
    [J]. SCIENCE, 2000, 290 (5489) : 107 - 111
  • [8] Evans E. A., 1980, MECH THERMODYNAMICS
  • [10] POLYMERIZED SURFACTANT VESICLES - NOVEL MEMBRANE MIMETIC SYSTEMS
    FENDLER, JH
    [J]. SCIENCE, 1984, 223 (4639) : 888 - 894